A type of iron ion Fe 3+ Doped spinel-structured fluorogallate near-infrared phosphors, their preparation methods, and their applications in medical flaw detection.

Abstract

The application provides a kind of iron ion Fe 3+ Doped spinel structure fluorogallate near-infrared fluorescent powder and its preparation method and medical flaw detection application.The iron ion Fe 3+ Doped spinel structure fluorogallate near-infrared fluorescent powder has the chemical formula MgGa2O4:xFe 3+ , yF ‑ ; wherein, 0.00025≤x≤0.016, 0.05≤y≤1.2. Respectively, the compound containing magnesium ion Mg 2+ , the compound containing gallium ion Ga 3+ , the compound containing fluorine ion F ‑ And the compound containing iron ion Fe 3+ As raw materials, the product is obtained by calcination treatment. The Fe 3+ Doped spinel structure fluorogallate near-infrared fluorescent powder can be applied in biomedical non-destructive flaw detection.

Description

Technical Field

[0001] This invention relates to the field of solid-state luminescent materials, and in particular to an iron ion Fe 3+ Doped spinel-structured fluorogallate near-infrared phosphors, their preparation methods, and their applications in medical flaw detection. Background Technology

[0002] Near-infrared light has wide applications in fields such as non-destructive testing of biological materials, non-destructive analysis of food, plant growth lighting, and night vision. With the rapid development of technology and the rapid deployment of the Internet of Things (IoT), near-infrared luminescent materials urgently need to be compatible with a large number of increasingly sophisticated portable devices. Therefore, the research and application of near-infrared luminescent materials has become a hot topic in the field of luminescence. Near-infrared phosphorus-based light-emitting diodes (NIR pc-LEDs) have become a focus of attention due to their small size, high efficiency, and tunable near-infrared emission. Currently, Cr... 3+ Doped phosphors are the preferred choice for broadband NIR emission because Cr 3+ It is quite sensitive to the influence of crystal field strength and coordination environment, exhibiting broadband emission in a weak eight-coordinate crystal field. Furthermore, Cr... 3+ Doped phosphors exhibit excellent absorption matching with commercial blue LED chips. However, on the one hand, Cr... 3+ Doped phosphors may be oxidized to Cr during the preparation process or under harsh conditions. 4+ Cr 5+ or Cr 6+ This increases energy loss from non-radiative transitions such as inter-ion energy transfer, ultimately leading to reduced luminescence efficiency; on the other hand, Cr 3+ The chromium toxicity of doped phosphors also limits their use in the biomedical field.

[0003] With Cr 3+ In comparison, Fe 3+ It possesses both environmental friendliness and biocompatibility, making its application prospects even broader. However, because Fe... 3+ It has very demanding requirements for the luminescent environment, and only a limited number of matrices are compatible with it, which has led to the current limited application of Fe... 3+ Research on its application in phosphors is relatively limited. Some studies have reported that MgGa2O4 lies between the normal and inverse spinel structures, and due to its rich content of inverse defects, it is suitable for Fe doping. 3+ Near-infrared long-afterglow phosphors were obtained; however, Fe... 3+ The doping of phosphors significantly limits their luminescence efficiency, thus failing to meet the requirements of phosphors for non-destructive testing applications in biomedicine. Therefore, existing technologies still need improvement. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide an iron ion-doped spinel structure fluorogallate near-infrared phosphor, its preparation method and its application in plant lighting, in order to solve the problems mentioned in the background art.

[0005] The technical solution of the present invention is as follows:

[0006] A type of iron ion Fe 3+ A method for preparing doped spinel-structured fluorogallate near-infrared phosphors includes the following steps:

[0007] Separately, Mg containing magnesium ions 2+ Compounds containing gallium ions Ga 3+ Compounds containing fluoride ions F - Compounds and compounds containing iron ions (Fe) 3+ The compound is used as a raw material, according to the chemical formula: MgGa2O4:xFe 3+ yF - Weigh the raw material according to the molar proportions of the four elements Mg, Ga, F, and Fe; where x is the Fe dopant. 3+ The molar fractions are taken as 0.00025 ≤ x ≤ 0.016, where y is the doped fluorine ion F. - The number of moles, taking 0.05 ≤ y ≤ 1.2;

[0008] The weighed raw materials are mixed and ground thoroughly, and then calcined to obtain the calcined product.

[0009] The calcined product was naturally cooled to room temperature, and then thoroughly ground again to obtain F. - Fe after repairing oxygen vacancies 3+ Near-infrared phosphors of fluorogallate with spinel structure.

[0010] Preferably, the calcination is carried out in an air atmosphere, the calcination temperature is 950-1400℃, and the calcination time is 5-15 hours.

[0011] Preferably, the one containing Mg 2+ The compound is any one or a combination of MgCO3, MgO, Mg(HCO3)2, and Mg(OH)2; containing Ga 3+ The compound is any one or a combination of Ga₂O₃, Ga(NO₃)₃, and GaF₃; containing Fe 3+ The compound is any one or more combinations of FeO, Fe2O3, and Fe3O4; containing F - The compound is any one or more combinations of NH4F, NH5F2, GaF3, and MgF2.

[0012] The present invention also provides Fe 3+ Doped spinel-structured fluorogallate near-infrared phosphor, with the chemical formula: MgGa2O4:xFe 3+ yF - Wherein, 0.00025≤x≤0.016, 0.05≤y≤1.2; the Fe 3+ Doped spinel-structured fluorogallate near-infrared phosphors possess F - Fe after repairing oxygen vacancies 3+ Doped spinel structure. The Fe... 3+ The doped spinel-structured fluorogallate near-infrared phosphor exhibits an excitation band in the 310–400 nm range; the Fe... 3+ The doped spinel-structured fluorogallate near-infrared phosphor exhibits the strongest emission peak at 740 nm to 750 nm under a 365 nm excitation wavelength.

[0013] Preferably, the Fe 3+ The chemical formula of the doped spinel-structured fluorogallate near-infrared phosphor is: MgGa₂O₄:0.2%Fe 3+ , 1F; the Fe 3+ The doped spinel-structured fluorogallate near-infrared phosphor exhibits a peak emission at 746 nm under a 365 nm excitation wavelength; the Fe... 3+ The doped spinel-structured fluorogallate near-infrared phosphors exhibited luminescence intensities at 363 K and 423 K that were 91.17% and 85.10% of their luminescence intensities at 30 °C, respectively.

[0014] The present invention also provides the Fe described above. 3+ Application of doped spinel-structured fluorogallate near-infrared phosphors in biomedical non-destructive testing.

[0015] Preferably, the Fe 3+ Doped spinel-structured fluorogallate near-infrared phosphors are mixed with silicone and then dotted onto the ultraviolet LED chip to obtain an NIR pc-LED device. The NIR pc-LED device is then used for non-destructive testing in biomedicine.

[0016] This invention has the following superior effects:

[0017] (1) The Fe of the present invention 3+ Doped near-infrared phosphors are environmentally friendly and biocompatible;

[0018] (2) The Fe of the present invention 3+ Doped near-infrared phosphors via F -Repairing the oxygen defect resulted in a 10 nm redshift of the emission peak to 746 nm, and the integrated intensity was increased to 15.6 times the original.

[0019] (3) The Fe of the present invention 3+ Doped near-infrared phosphors can maintain 85.10% of the luminous intensity at 30°C at a temperature of 423K, meeting the requirements for LED device use.

[0020] (4) The Fe of the present invention 3+ The raw materials required for the preparation of doped near-infrared phosphors are low-cost, and the preparation method is simple and effective. Attached Figure Description

[0021] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Some specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings in an exemplary and non-limiting manner. The same reference numerals in the drawings indicate the same or similar parts or components. Those skilled in the art should understand that these drawings are not necessarily drawn to scale. In the drawings:

[0022] Figure 1 X-ray diffraction patterns of the phosphor samples prepared according to Examples 1-13;

[0023] Figure 2 The excitation spectrum of the phosphor sample prepared according to Example 11 at a detection wavelength of 746 nm;

[0024] Figure 3 The emission spectrum of the phosphor sample prepared according to Example 11 at an excitation wavelength of 365 nm;

[0025] Figure 4 The emission spectrum peak shape and intensity changes of the fluorescent sample prepared according to Example 11 at an excitation wavelength of 365 nm in the temperature range of 303–473 K;

[0026] Figure 5 The image shows the blood vessels of the little finger captured by a near-infrared camera under the illumination of a NIR pc-LED encapsulated in a fluorescent sample prepared according to Example 11. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0028] Example 1: Preparation of MgGa2O4:0.2mol%Fe 3+ 0.05 mol F- fluorescent powder

[0029] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.05 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.07800 g of MgO, 0.37488 g of Ga₂O₃, 0.00312 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and thoroughly ground in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1300°C for 6 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 0.05 mol F - .

[0030] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0031] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 8 times that of the sample before defect repair.

[0032] Example 2: Preparation of MgGa2O4:0.2mol%Fe 3+ 0.1 mol F - fluorescent powder

[0033] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.1 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.07600 g of MgO, 0.37488 g of Ga₂O₃, 0.00624 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and thoroughly ground in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1150°C for 7.5 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 0.1 mol F - .

[0034] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0035] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 9.4 times that of the sample before defect repair.

[0036] Example 3: Preparation of MgGa2O4:0.2mol%Fe 3+ 0.2 mol F - fluorescent powder

[0037] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.2 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.07200 g of MgO, 0.37488 g of Ga₂O₃, 0.01248 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and ground thoroughly in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1000°C for 9.5 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 0.2 mol F - .

[0038] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0039] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 10 times that of the sample before defect repair.

[0040] Example 4: Preparation of MgGa2O4:0.2mol%Fe 3+ 0.3 mol F - fluorescent powder

[0041] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.3 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.06800 g of MgO, 0.37488 g of Ga₂O₃, 0.01872 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and thoroughly ground in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1050 °C for 9 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 0.3 mol F - .

[0042] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0043] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 10.4 times that of the sample before defect repair.

[0044] Example 5: Preparation of MgGa2O4:0.2mol%Fe 3+ 0.4 mol F - fluorescent powder

[0045] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.4 mol F - Based on the stoichiometric ratios of the corresponding elements, MgO: 0.06400g, Ga2O3: 0.37488g, MgF2: 0.02496g, and Fe2O3: 0.00032g were weighed out and ground thoroughly in an agate mortar. The mixture was then placed in a crucible and calcined in air at 950℃ for 10 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa2O4:0.2mol%Fe. 3+ 0.4 mol F - .

[0046] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0047] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 11.2 times that of the sample before defect repair.

[0048] Example 6: Preparation of MgGa2O4:0.2mol%Fe 3+ 0.5 mol F - fluorescent powder

[0049] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.5 mol F -Based on the stoichiometric ratios of the corresponding elements, 0.06000 g of MgO, 0.37488 g of Ga₂O₃, 0.03120 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and thoroughly ground in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1100°C for 8 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 0.5 mol F - .

[0050] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0051] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 11.5 times that of the sample before defect repair.

[0052] Example 7: Preparation of MgGa2O4:0.2 mol% Fe 3+ 0.6 mol F - fluorescent powder

[0053] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.6 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.05600 g of MgO, 0.37488 g of Ga₂O₃, 0.03744 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and thoroughly ground in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1200°C for 7 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 0.6 mol F - .

[0054] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0055] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 11.5 times that of the sample before defect repair.

[0056] Example 8: Preparation of MgGa2O4:0.2mol%Fe 3+ 0.7 mol F- fluorescent powder

[0057] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ The stoichiometric ratios of the corresponding elements in 0.7 mol F- were determined by weighing out 0.05200 g of MgO, 0.37488 g of Ga2O3, 0.04368 g of MgF2, and 0.00032 g of Fe2O3. These were then thoroughly ground in an agate mortar and placed in a crucible for calcination in air at 1250 °C for 7.5 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa2O4:0.2 mol%Fe. 3+ 0.7 mol F - .

[0058] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0059] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 12.3 times that of the sample before defect repair.

[0060] Example 9: Preparation of MgGa2O4:0.2mol%Fe 3+ 0.8 mol F - fluorescent powder

[0061] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.8 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.04800 g of MgO, 0.37488 g of Ga₂O₃, 0.04992 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and ground thoroughly in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 900°C for 9 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 0.8 mol F - .

[0062] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0063] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 14 times that of the sample before defect repair.

[0064] Example 10: Preparation of MgGa2O4:0.2 mol% Fe 3+ 0.9 mol F - fluorescent powder

[0065] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 0.9 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.04400 g of MgO, 0.37488 g of Ga₂O₃, 0.05616 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and thoroughly ground in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1250°C for 8 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 0.9 mol F - .

[0066] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0067] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 14.6 times that of the sample before defect repair.

[0068] Example 11: Preparation of MgGa2O4:0.2 mol% Fe 3+ 1.0 mol F - fluorescent powder

[0069] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 1.0 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.04000 g of MgO, 0.37488 g of Ga₂O₃, 0.06240 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and ground thoroughly in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1300°C for 7 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ , 1.0 mol F-.

[0070] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0071] See appendix Figure 2 The excitation spectrum of the phosphor sample prepared according to the scheme of this embodiment shows a unique excitation band in the range of 310-400 nm.

[0072] See appendix Figure 3 The emission spectrum of the phosphor sample prepared according to the scheme of this embodiment at an excitation wavelength of 365nm shows that the strongest emission peak is at 746nm, and the integrated intensity is increased to 15.6 times that of the sample before defect repair.

[0073] See appendix Figure 4 The emission spectrum peak shape and intensity changes of the phosphor sample prepared according to the scheme of this embodiment are shown in the temperature range of 303 to 473 K at an excitation wavelength of 365 nm. It can be observed that the luminescence intensity at 30 °C is maintained at 91.17% and 85.10% at 363 K and 423 K, respectively, which meets the requirements for the use of NIR-LED devices.

[0074] See appendix Figure 5 The image shows the blood vessels of the little finger captured by a near-infrared camera under the illumination of a NIR-LED encapsulated in a phosphor sample prepared according to the scheme of this embodiment.

[0075] Example 12: Preparation of MgGa2O4:0.2mol%Fe 3+ 1.1 mol F-phosphor

[0076] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ The stoichiometric ratios of the corresponding elements in 1.1 mol F- were determined by weighing out 0.03600 g of MgO, 0.37488 g of Ga2O3, 0.06864 g of MgF2, and 0.00032 g of Fe2O3. These were then thoroughly ground in an agate mortar and placed in a crucible for calcination in air at 1400℃ for 5 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa2O4:0.2 mol%Fe. 3+ 1.1 mol F-.

[0077] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0078] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 13.1 times that of the sample before defect repair.

[0079] Example 13: Preparation of MgGa2O4:0.2mol%Fe 3+ 1.2 mol F - fluorescent powder

[0080] According to the general chemical formula MgGa2O4:0.2mol%Fe 3+ 1.2 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.03200 g of MgO, 0.37488 g of Ga₂O₃, 0.07488 g of MgF₂, and 0.00032 g of Fe₂O₃ were weighed out and ground thoroughly in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 950°C for 15 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.2 mol%Fe. 3+ 1.2 mol F - .

[0081] See appendix Figure 1 The X-ray diffraction pattern of the phosphor sample prepared according to the scheme of this embodiment is shown. The results show that the crystal phase of the prepared material is indeed MgGa2O4.

[0082] The excitation spectrum, emission spectrum, half-maximum width, and thermal stability of the phosphor sample prepared according to the scheme of this embodiment are similar to those of Example 11, and the integrated intensity is increased to 12.3 times that of the sample before defect repair.

[0083] Example 14: Preparation of MgGa2O4:0.025mol%Fe 3+ 1.0 mol F - fluorescent powder

[0084] According to the general chemical formula MgGa2O4:0.025mol%Fe 3+ 1.0 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.04000 g of MgO, 0.37488 g of Ga₂O₃, 0.06240 g of MgF₂, and 0.00004 g of Fe₂O₃ were weighed out and ground thoroughly in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1300°C for 7 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.025 mol%Fe. 3+ 1.0 mol F - 。

[0085] Example 15: Preparation of MgGa2O4:0.05mol%Fe 3+ 1.0 mol F - fluorescent powder

[0086] According to the general chemical formula MgGa2O4:0.05mol%Fe 3+ 1.0 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.04000 g of MgO, 0.37488 g of Ga₂O₃, 0.06240 g of MgF₂, and 0.00008 g of Fe₂O₃ were weighed out and thoroughly ground in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1300°C for 7 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.05 mol%Fe. 3+ 1.0 mol F - 。

[0087] Example 16: Preparation of MgGa2O4:0.1 mol% Fe 3+ 1.0 mol F - fluorescent powder

[0088] According to the general chemical formula MgGa2O4:0.1mol%Fe 3+ 1.0 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.04000 g of MgO, 0.37488 g of Ga₂O₃, 0.06240 g of MgF₂, and 0.00016 g of Fe₂O₃ were weighed out and ground thoroughly in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1300°C for 7 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.1 mol%Fe. 3+ 1.0 mol F - 。

[0089] Example 17: Preparation of MgGa2O4:0.4mol%Fe 3+ 1.0 mol F - fluorescent powder

[0090] According to the general chemical formula MgGa2O4:0.4mol%Fe 3+ 1.0 mol F -Based on the stoichiometric ratios of the corresponding elements, 0.04000 g of MgO, 0.37488 g of Ga₂O₃, 0.06240 g of MgF₂, and 0.00064 g of Fe₂O₃ were weighed out and ground thoroughly in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1300°C for 7 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.4 mol%Fe. 3+ 1.0 mol F - 。

[0091] Example 18: Preparation of MgGa2O4:0.8 mol% Fe 3+ 1.0 mol F - fluorescent powder

[0092] According to the general chemical formula MgGa2O4:0.8mol%Fe 3+ 1.0 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.04000 g of MgO, 0.37488 g of Ga₂O₃, 0.06240 g of MgF₂, and 0.00128 g of Fe₂O₃ were weighed out and thoroughly ground in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1300°C for 7 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:0.8 mol%Fe. 3+ 1.0 mol F - 。

[0093] Example 19: Preparation of MgGa2O4:1.6mol%Fe 3+ 1.0 mol F - fluorescent powder

[0094] According to the general chemical formula MgGa2O4:1.6mol%Fe 3+ 1.0 mol F - Based on the stoichiometric ratios of the corresponding elements, 0.04000 g of MgO, 0.37488 g of Ga₂O₃, 0.06240 g of MgF₂, and 0.00256 g of Fe₂O₃ were weighed out and ground thoroughly in an agate mortar. The resulting powder was then placed in a crucible and calcined in air at 1300°C for 7 hours. After natural cooling to room temperature, the sample was removed, yielding the target product MgGa₂O₄:1.6 mol%Fe. 3+ 1.0 mol F - 。

[0095] Example 20: The phosphor prepared according to the scheme of Example 11 is used in the fabrication of NIR pc-led devices.

[0096] Mix silicone rubber agents A and B in a 1:1 ratio, then add MgGa2O4:0.2mol%Fe. 3+ 1.0 mol F - The phosphors are thoroughly mixed, and then the mixture is dotted onto a 365nm ultraviolet chip and placed in an oven at 100°C for 1-3 hours to completely remove air bubbles, thus obtaining an NIR pc-LED device. The above description is only a partial embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A Fe 3+ A method for preparing doped spinel-structured fluorogallate near-infrared phosphors, characterized in that, Includes the following steps: Separately, Mg containing magnesium ions 2+ Compounds containing gallium ions Ga 3+ Compounds containing fluoride ions (F-) and iron ions (Fe-) 3+ The compound is used as a raw material, according to the chemical formula: MgGa2O4:xFe 3+ yF - Weigh the raw material according to the molar proportions of the four elements Mg, Ga, F, and Fe; where x is the Fe dopant. 3+ The molar fractions are taken as 0.00025 ≤ x ≤ 0.016, where y is the doped fluorine ion F. - The number of moles, taking 0.05 ≤ y ≤ 1.2; After weighing and mixing the raw materials and grinding them thoroughly, the mixture is calcined in air at a temperature of 950-1400℃ for 5-15 hours to obtain the calcined product. The calcined product was naturally cooled to room temperature, and then thoroughly ground again to obtain F. - Fe after repairing oxygen vacancies 3+ Doped spinel-structured fluorogallate near-infrared phosphor.

2. The Fe according to claim 1 3+ A method for preparing doped spinel-structured fluorogallate near-infrared phosphors, characterized in that, The one containing Mg 2+ The compound is any one or a combination of MgCO3, MgO, Mg(HCO3)2, and Mg(OH)2; containing Ga 3+ The compound is any one or a combination of Ga₂O₃, Ga(NO₃)₃, and GaF₃; containing Fe 3+ The compound is any one or more combinations of FeO, Fe2O3, and Fe3O4; containing F - The compound is any one or more combinations of NH4F, NH5F2, GaF3, and MgF2.

3. A Fe 3+ Doped spinel-structured fluorogallate near-infrared phosphor, characterized in that, The chemical formula is: MgGa2O4:xFe 3+ yF - Wherein, 0.00025≤x≤0.016, 0.05≤y≤1.2; the Fe 3+ Doped spinel-structured fluorogallate near-infrared phosphors possess F-repaired Fe... 3+ It has a spinel structure and an excitation band in the range of 310–400 nm. The strongest emission peak at an excitation wavelength of 365 nm is in the range of 740–750 nm, and the luminescence intensity at 423 K is 85.10% of its luminescence intensity at 30 °C.

4. The Fe as described in claim 3 3+ Application of doped spinel-structured fluorogallate near-infrared phosphors in biomedical non-destructive testing.

5. The application as described in claim 4, characterized in that, Includes the following steps: The Fe 3+ Doped spinel-structured fluorogallate near-infrared phosphors are mixed with silicone and then dotted onto a UV LED chip to obtain an NIR pc-LED device. The NIR pc-LED device is then used for non-destructive testing in biomedicine.

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